Modifications of Surface Properties of Beta Ti by Laser Gas Diffusion Nitriding

Beta-type Ti-alloy is a promising biomedical implant material as it has a low Young’s modulus and is also known to have inferior surface hardness. Various surface treatments can be applied to enhance the surface hardness. Physical vapor deposition and chemical vapor deposition are two examples of this but these techniques have limitations such as poor interfacial adhesion and high distortion. Laser surface treatment is a relatively new surface modification method to enhance the surface hardness but its application is still not accepted by the industry. The major problem of this process involves surface melting which results in higher surface roughness after the laser surface treatment. This paper will report the results achieved by a 100 W continuous wave (CW) fiber laser for laser surface treatment without the surface being melted. Laser processing parameters were carefully selected so that the surface could be treated without surface melting and thus the surface finish of the component could be maintained. The surface and microstructural characteristics of the treated samples were examined using x-ray diffractometry, optical microscopy, three-dimensional surface profile and contact angle measurements, and nanoindentation test.

Continuous flow hydroformylation using supported ionic liquid phase catalysts with carbon dioxide as a carrier.

A supported ionic liquid phase (SILP) catalyst prepared from [PrMIM][Ph2P(3-C6H4SO3)] (PrMIM = 1-propyl-3-methylimidazolium), [Rh(CO)(2)(acac)] (acacH = 2,4-pentanedione) [OctMIM]NTf2 (OctMIM = 1-n-octyl-3-methylimidazolium, Tf = CF3SO2) and microporous silica has been used for the continuous flow hydroformylation of 1-octene in the presence of compressed CO2. Statistical experimental design was used to show that the reaction rate is neither much affected by the film thickness (IL loading) nor by the syngas: substrate ratio. However, a factor-dependent interaction between the syngas: substrate ratio and film thickness on the reaction rate was revealed. Increasing the substrate flow led to increased reaction rates but lower overall yields. One of the most important parameters proved to be the phase behaviour of the mobile phase, which was studied by varying the reaction pressure. At low CO2 pressures or when N-2 was used instead of CO2 rates were low because of poor gas diffusion to the catalytic sites in the SILP. Furthermore, leaching of IL and Rh was high because the substrate is liquid and the IL had been designed to dissolve in it. As the CO2 pressure was increased, the reaction rate increased and the IL and Rh leaching were reduced, because an expanded liquid phase developed. Due to its lower viscosity the expanded liquid allows better transport of gases to the catalyst and is a poorer solvent for the IL and the catalyst because of its reduced polarity. Above 100 bar (close to the transition to a single phase at 106 bar), the rate of reaction dropped again with increasing pressure because the flowing phase becomes a better and better solvent for the alkene, reducing its partitioning into the IL film. Under optimised conditions, the catalyst was shown to be stable over at least 40 h of continuous catalysis with a steady state turnover frequency (TOF, mol product (mol Rh)(-1)) of 500 h(-1) at low Rh leaching (0.2 ppm). The selectivity of the catalyst was not much affected by the variation of process parameters. The linear: branched (1:b) ratios were ca. 3, similar to that obtained using the very same catalyst in conventional organic solvents.

Theoretical and experimental correlations of gas dissolution, diffusion, and thermodynamic properties in determination of gas permeability and selectivity in supported ionic liquid membranes

Supported ionic liquid membranes (SILMs) has the potential to be a new technological platform for gas/organic vapour separation because of the unique non-volatile nature and discriminating gas dissolution properties of room temperature ionic liquids (ILs). This work starts with an examination of gas dissolution and transport properties in bulk imidazulium cation based ionic liquids [C_nmim][NTf2] (n = 2.4, 6, 8.10) from simple gas H₂, N₂, to polar CO₂, and C₂H₆, leading to a further analysis of how gas dissolution and diffusion are influenced by molecular specific gas-SILMs interactions, reflected by differences in gas dissolution enthalpy and entropy. These effects were elucidated again during gas permeation studies by examining how changes in these properties and molecular specific interactions work together to cause deviations from conventional solution–diffusion theory and their impact on some remarkably contrasting gas perm-selectivity performance. The experimental perm-selectivity for all tested gases showed varied and contrasting deviation from the solution–diffusion, depending on specific gas-IL combinations. It transpires permeation for simpler non-polar gases (H₂, N₂) is diffusion controlled, but strong molecular specific gas-ILs interactions led to a different permeation and selectivity performance for C₂H₆ and CO₂. With exothermic dissolution enthalpy and large order disruptive entropy, C₂H₆ displayed the fastest permeation rate at increased gas phase pressure in spite of its smallest diffusivity among the tested gases. The C₂H₆ gas molecules “peg” on the side alkyl chain on the imidazulium cation at low concentration, and are well dispersed in the ionic liquids phase at high concentration. On the other hand strong CO₂-ILs affinity resulted in a more prolonged “residence time” for the gas molecule, typified by reversed CO₂/N₂ selectivity and slowest CO₂ transport despite CO₂ possess the highest solubility and comparable diffusivity in the ionic liquids. The unique transport and dissolution behaviour of CO₂ are further exploited by examining the residing state of CO₂ molecules in the ionic liquid phase, which leads to a hypothesis of a condensing and holding capacity of ILs towards CO₂, which provide an explanation to slower CO₂ transport through the SILMs. The pressure related exponential increase in permeations rate is also analysed which suggests a typical concentration dependent diffusion rate at high gas concentration under increased gas feed pressure. Finally the strong influence of discriminating and molecular specific gas-ILs interactions on gas perm-selectivity performance points to future specific design of ionic liquids for targeted gas separations.

Fixed-node diffusion Monte Carlo computations for closed-shell jellium spheres

Fixed-node diffusion Monte Carlo computations are used to determine the ground state energy and electron density for jellium spheres with up to N = 106 electrons and background densities corresponding to the electron gas parameter 1 less than or equal to r(s)less than or equal to5.62. We analyze the density and size dependence of the surface energy, and we extrapolate our data to the thermodynamic limit. The results agree well with the predictions of density functional computations using the local density approximation. In the case of N = 20, we extend our computation to higher densities and identify a transition between atomic- and jelliumlike nodal structures occurring at the background density corresponding to r(s)=0.13. In this case the local density approximation is unable to reproduce the changes in the correlation energy due to the discontinuous transition in the ground state nodal structure. We discuss the relevance of our results for nonlocal approximations to density functional theory.

Neutral gas depletion mechanisms in dense low-temperature argon plasmas

Neutral gas depletion mechanisms are investigated in a dense low-temperature argon plasma-an inductively coupled magnetic neutral loop (NL) discharge. Gas temperatures are deduced from the Doppler profile of the 772.38 nm line absorbed by argon metastable atoms. Electron density and temperature measurements reveal that at pressures below 0.1 Pa, relatively high degrees of ionization (exceeding 1%) result in electron pressures, p(e) = kT(e)n(e), exceeding the neutral gas pressure. In this regime, neutral dynamics has to be taken into account and depletion through comparatively high ionization rates becomes important. This additional depletion mechanism can be spatially separated due to non-uniform electron temperature and density profiles (non-uniform ionization rate), while the gas temperature is rather uniform within the discharge region. Spatial profiles of the depletion of metastable argon atoms in the NL region are observed by laser induced fluorescence spectroscopy. In this region, the depletion of ground state argon atoms is expected to be even more pronounced since in the investigated high electron density regime the ratio of metastable and ground state argon atom densities is governed by the electron temperature, which peaks in the NL region. This neutral gas depletion is attributed to a high ionization rate in the NL zone and fast ion loss through ambipolar diffusion along the magnetic field lines. This is totally different from what is observed at pressures above 10 Pa where the degree of ionization is relatively low (

Use of room temperature ionic liquids in gas sensor design

The attainable steady-state limiting currents and time responses of membrane-covered and membrane-independent gas sensors incorporating different electrode and electrolyte materials have been compared. A new design comprising a membrane-free microelectrode modified with a thin layer of a room temperature ionic liquid is considered. While the use of ionic liquid as electrolyte eliminates the need for a membrane and added supporting electrolyte, the slower diffusion of analyte within the more viscous medium results in slower time responses. Such sensors do, however, have potential application in more extreme operating conditions, such as high temperature and pressure, where traditional solvents would volatise.

Turbulent diffusion and mixing in interstellar dark clouds with adsorption onto grains

This paper reports the results of models of dark cloud chemistry incorporating a depth dependent density distribution with diffusive mixing and adsorption onto grains. The model is based on the approach taken by Xie et al. (1995), with the addition of grain accretion effects. Without diffusion, the central regions of the cloud freeze out in less than 10(7) years. Freeze-out time is dependent on density, so the diffuse outer region of the cloud remains abundant in gas for about an order of magnitude longer. We find that fairly small amounts of diffusive mixing can delay freeze-out at the centre of the model cloud for a time up to an order of magnitude greater than without diffusion, due to material diffusing inward from the edges of the cloud. The gas-phase lifetime of the cloud core can thus be increased by up to an order of magnitude or more by this process. We have run three different grain models with various diffusion coefficients to investigate the effects of changing the sticking parameters.

SO2 Saturation of the Room Temperature Ionic Liquid [C(2)mim][NTf2] Much Reduces the Activation Energy for Diffusion

The physical effect of high concentrations of reversibly dissolved SO2 on [C(2)mim][NTf2] was examined using cyclic voltammetry, chronoamperometry, and ESR spectroscopy. Cyclic voltammetry of the oxidation of solutions of ferrocene, N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD), and chloride in the room temperature ionic liquid (RTIL) 1-ethyl-3-methylimidazolium bis(trifluoromethanesufonyl)imide ([C(2)mim][NTf2]) reveals an increase in limiting current of each species corresponding to the addition of increasing concentrations of sulfur dioxide. Quantitative chronoamperometry reveals an increase in each species' diffusion coefficient with SO2 concentration. When chronoamperometric data were obtained for ferrocene in [C(2)mim][NTf2] at a range of temperatures, the translational diffusion activation energy (29.0 +/- 0.5 kJ mol(-1)) was found to be in good agreement with previous studies. Adding SO2 results in apparent near-activationless translational diffusion. A significant decrease in the activation energy of rotational diffusion with the SO2 saturation of a 2,2,6,6-tetramethyl-1-piperidinyloxyl (TEMPO) solution in [C(2)mim][NTf2] (29.9 +/- 2.0 to 7.7 +/- 5.3 kJ mol(-1)) was observed using electron spin resonance (ESR) spectroscopy. The reversible physical absorption Of SO2 by [C(2)mim][NTf2] should have no adverse effect on the ability of that ionic liquid to be employed as a solvent in an electrochemical gas sensor, and it is possible that the SO2-mediated reduction of RTIL viscosity could have intrinsic utility.

Effect of resonance frequency, power input, and saturation gas type on the oxidation efficiency of an ultrasound horn

The sonochemical oxidation efficiency (eta(ox)) of a commercial titanium alloy ultrasound horn has been measured using potassium iodide as a dosimeter at its main resonance frequency (20 kHz) and two higher resonance frequencies (41 and 62 kHz). Narrow power and frequency ranges have been chosen to minimise secondary effects such as changing bubble stability, and time available for radical diffusion from the bubble to the liquid. The oxidation efficiency, eta(ox), is proportional to the frequency and to the power transmitted to the liquid (275 mL) in the applied power range (1-6 W) under argon. Luminol radical visualisation measurements show that the radical generation rate increases and a redistribution of radical producing zones is achieved at increasing frequency. Argon, helium, air, nitrogen, oxygen, and carbon dioxide have been used as saturation gases in potassium iodide oxidation experiments. The highest eta(ox) has been observed at 5 W under air at 62 kHz. The presence of carbon dioxide in air gives enhanced nucleation at 41 and 62 kHz and has a strong influence on eta(ox). This is supported by the luminol images, the measured dependence of eta(ox). on input power, and bubble images recorded under carbon dioxide. The results give insight into the interplay between saturation gas and frequency, nucleation, and their effect on eta(ox). (C) 2010 Elsevier B.V. All rights reserved.

MODELED DIFFUSION-CONTROLLED RESPONSE AND RECOVERY BEHAVIOR OF A NAKED OPTICAL FILM SENSOR WITH A HYPERBOLIC-TYPE RESPONSE TO ANALYTE CONCENTRATION

The diffusion-controlled response and recovery behaviour of a naked optical film sensor (i.e., with no protective membrane) with a hyperbolic-type response [i.e., S0/S = (1 + Kc), where S is the measured value of the absorbance or luminescence intensity of one form of the sensor dye in the presence of the analyte, S0 is the observed value of S in the absence of analyte and K is a constant] to changes in analyte concentration, c, in a system under test is approximated using a simple model, and described more accurately using a numerical model; in both models it is assumed that the system under test represents an infinite reservoir. Each model predicts the variations in the response and recovery times of such an optical sensor, as a function of the final external analyte concentration, the film thickness (I) and the analyte diffusion coefficient (D). From an observed signal versus time profile for a naked optical film sensor it is shown how values for K and D/I2 can be extracted using the numerical model. Both models provide a qualitative description of the often cited asymmetric nature of the response and recovery for hyperbolic-type response naked optical film sensors. It is envisaged that the models will help in the interpretation of the response and recovery behaviour exhibited by many naked optical film sensors and might be especially apposite when the analyte is a gas.

Using temporal analysis of products and flux response technology to determine diffusion coefficients in catalytic monoliths

The importance of accurately measuring gas diffusivity in porous materials has led to a number of methods being developed. In this study the Temporal Analysis of Products (TAP) reactor and Flux Response Technology (FRT) have been used to examine the diffusivity in the washcoat supported on cordierite monoliths. Herein, the molecular diffusion of propane within four monoliths with differently prepared alumina/CeZrOx washcoats was investigated as a function of temperature. Moment-based analysis of the observed TAP responses led to the calculation of the apparent intermediate gas constant, Kp, that characterises adsorption into the mesoporous network and apparent time delay, tapp, that characterises residence time in the mesoporous network. Additionally, FRT has been successfully adapted as an extensive in situ perturbation technique in measuring intraphase diffusion coefficients in the washcoats of the same four monolith samples. The diffusion coefficients obtained by moment-based analysis of TAP responses are larger than the coefficients determined by zero length column (ZLC) analysis of flux response profiles with measured values of the same monolith samples between 20 and 100 °C ranging from 2–5×10^-9 m² s^-1 to 4–8×10^-10 m² s^-1, respectively. The TAP and FRT data, therefore, provide a range of the lower and upper limits of diffusivity, respectively. The reported activation energies and diffusivities clearly correlate with the difference in the washcoat structure of different monolith samples.

Probing Bias-Dependent Electrochemical Gas-Solid Reactions in (LaxSr1-x)CoO3-delta Cathode Materials

Spatial variability of bias-dependent electrochemical processes on a (La0.5Sr0.5)(2)CoO4 +/- modified (LaxSr1-x)CoO3- surface is studied using first-order reversal curve method in electrochemical strain microscopy (ESM). The oxygen reduction/evolution reaction (ORR/OER) is activated at voltages as low as 3-4 V with respect to bottom electrode. The degree of bias-induced transformation as quantified by ESM hysteresis loop area increases with applied bias. The variability of electrochemical activity is explored using correlation analysis and the ORR/OER is shown to be activated in grains at relatively low biases, but the final reaction rate is relatively small. At the same time, at grain boundaries, the onset of reaction process corresponds to larger voltages, but limiting reactivity is much higher. The reaction mechanism in ESM of mixed electronic-ionic conductor is further analyzed. These studies both establish the framework for probing bias-dependent electrochemical processes in solids and demonstrate rich spectrum of electrochemical transformations underpinning catalytic activity in cobaltites.

Evaluation of a simple disposable microband electrode device for amperometric gas sensing

We report a simple and facile methodology for constructing Pt (6.3 mm x 50 mu m) and Cu (6.3 mm x 30 mu m) annular microband electrodes for use in room temperature ionic liquids (RTILs) and propose their use for amperometric gas sensing. The suitability of microband electrodes for use in electrochemical analysis was examined in experiments on two systems. The first system studied to validate the electrochemical responses of the annular microband electrode was decamethylferrocene (DmFc), as a stable internal reference probe commonly used in ionic liquids, in [Pmim][NTf2], where the diffusion coefficients of DmFc and DmFc(+) and the standard electron rate constant for the DmFc/DmFc(+) couple were determined through fitting chronoamperometric and cyclic voltammetric responses with relevant simulations. These values are independently compared with those collected from a commercially available Pt microdisc electrode with excellent agreement. The second system focuses on O-2 reduction in [Pmim][NTf2], which is used as a model for gas sensing. The diffusion coefficients of O-2 and O-2(-) and the electron transfer rate constant were again obtained using chronoamperometry and cyclic voltammetry, along with simulations. Results determined from the microbands are again consistent to those evaluated from the Pt microdisc electrode when compared these results from home-made microband and commercially available microdisc electrodes. These observations indicate that the fabricated annular microband electrodes are suitable for quantitative measurements. Further the successful use of the Cu electrodes in the O-2 system suggests a cheap disposable sensor for gas detection. (C) 2013 Elsevier B.V. All rights reserved.

A density functional theory study of hydrogen dissociation and diffusion at the perimeter sites of Au/TiO2

Reactivity of supported gold catalysts is a hot topic in catalysis for many years. This communication reports an investigation on the dissociation of molecular hydrogen at the perimeter sites of Au/TiO2 and the spillover of hydrogen atoms from the gold to the support using density functional theory calculations. It is found that the heterolytic dissociation is favoured in comparison with homolytic dissociation of molecular hydrogen at the perimeter sites. However, the surface oxygen of the rutile TiO2(110) surface at these sites can be readily passivated by the formed OH, suggesting that further dissociation of molecular hydrogen may occur at pure gold sites.

TAP Reactor Development and Application in the Kinetic Characterization of Catalysts for Heterogeneously Catalyzed Gas Phase Reactions

This manuscript describes the application and further development of the TAP technique in kinetic characterization of heterogeneous catalysis. The major application of TAP systems is to study mechanisms, kinetics and transport phenomena in heterogeneous catalysis, all of which is made possible by the sub-millisecond time resolution. Furthermore, the kinetic information obtained can be used to gain an insight into the mechanism occurring over the catalyst system. This is advantageous as heterogeneous catalysts with an improved efficiency can be developed as a result. TAP kinetic studies are carried out at low pressure (~1x10-7 mbar) and TAP pulses are sufficiently small (1013-1015 molecules) so as to maintain this low pressure. The use of a small number of molecules in comparison to the total number of active sites means the state of the catalyst remains relatively unchanged. The use of the low intensity pulses also makes the pressure gradient negligible and so allows the TAP reactor system to operate in the Knudsen Diffusion regime, where gas-gas reactions are eliminated. Hence only gas-catalyst reactions are investigated and, by the use of moment analysis of observed exit flow, rate constants of elementary steps of the reaction can be obtained.

In this manuscript, two attempts to further the TAP technique are reported. Firstly, the work undertaken at QUB to attempt to control the number of molecules of condensable reagents that can be pulsed during a TAP pulse experiment is disclosed. Secondly, a collaborative project with SAI Ltd Manchester is discussed in a separate chapter, where technical details and validation of a customised time of flight mass spectrometer (ToF MS) for the QUB TAP-1 system are reported. A collaborative project with Cardiff Catalysis Institute focusing on the study of CO oxidation over hopcalite catalysts is also reported. The analysis of the experimental results has provided an insight into the possible mechanism of the oxidation of CO over these catalysts. A correction function has also been derived which accounts for the adsorption of reactant molecules over inert materials that are used for the reactor packing in TAP experiments. This function was then applied to the selective reduction of O2 in a H2 rich ethene feed, so that more accurate TAP moment based analysis could be conducted.